WO1997014663A1 - Procede de fabrication de materiaux refractaires - Google Patents

Procede de fabrication de materiaux refractaires Download PDF

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Publication number
WO1997014663A1
WO1997014663A1 PCT/GB1996/002546 GB9602546W WO9714663A1 WO 1997014663 A1 WO1997014663 A1 WO 1997014663A1 GB 9602546 W GB9602546 W GB 9602546W WO 9714663 A1 WO9714663 A1 WO 9714663A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
phenolic resin
refractory
aldehyde
mixture
Prior art date
Application number
PCT/GB1996/002546
Other languages
English (en)
Inventor
Jason Robert Brewer
Andrew James Phillipps
Alison Mary Wagland
Frank Dillon
Original Assignee
Cookson Group Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cookson Group Plc filed Critical Cookson Group Plc
Priority to AU73127/96A priority Critical patent/AU7312796A/en
Publication of WO1997014663A1 publication Critical patent/WO1997014663A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers

Definitions

  • the present invention relates to a process for the manufacture of refractory articles and, in particular, to a process for the manufacture of carbon bonded refractory articles which are of particular use in the continuous casting of steel.
  • the manufacture of refractory articles for use in furnaces has involved the use of various binders to bind refractory materials together, the mixture of refractory material and binder being subjected to compression moulding to the desired shape and subsequent heat treatment, usually heating to temperatures in excess of 500°C, in order to carbonise the binder.
  • a binder which was historically used was pitch which suffers, however, from the disadvantages that it is a hazard to health since it is a suspected carcinogen.
  • carbon bonded refractory materials have been manufactured using phenolic resins which possess several advantages, the most important being that they have a high carbon yield, a good oxidation resistance and they produce components with a high fracture resistance.
  • Solid phenolic resins are preferred for use since they have a long shelf life, but they have to be dissolved in a solvent during the manufacturing process.
  • a solvent for the phenolic resins which is widely used in the industry is furfural but there are significant toxicity problems associated with the use of this solvent. The material is toxic by inhalation and can be absorbed through the skin. There is also evidence that it can cause mutagenic and carcinogenic effects in laboratory animals. Accordingly, significant precautions have to be taken to handle furfural.
  • EP-A-0276377 discloses the use of a binder system comprising a phenolic resin dissolved in a solvent mixture comprising a high density boiling point solvent and a low boiling point solvent, the high boiling point solvent preferably being selected from dibutyl phthalate, onoethylene glycol or furfuryl alcohol and the low boiling point solvent preferably being methanol.
  • this solvent mixture typically produces refractory articles of a lower quality than those produced using furfural.
  • the present invention provides a process for the manufacture of shaped refractory articles, which process comprises mixing one or more powdered refractory materials with a curable phenolic resin and adding an aldehyde as a solvent for the curable phenolic resin to the mixture, or adding a curable phenolic resin dissolved in an aldehyde solvent to the refractory powdered material(s), the aldehyde solvent comprising a compound of the general formula:
  • an aldehyde as defined above is used as a solvent for the curable phenolic resin and replaces the solvents, such as furfural, which have previously been used in the art.
  • Preferred solvents for use in the present invention are benzaldehyde, salicylaldehyde or anisaldehyde, or mixtures thereof.
  • the aldehyde solvent may also be mixed with other solvents which are not aldehydes, if desired.
  • the amount of the aldehyde solvent employed will generally be that amount required to reduce the viscosity of the mix during the processing stage to between 5 and 20 poise at the mixing temperature. The viscosity is a function of the mixing temperature and the amount of solvent employed, higher temperatures resulting in lower viscosities and greater amounts of solvent also resulting in lower viscosities.
  • Furfural as a solvent used in the prior art is known to react with phenolic resins and this reaction increases the viscosity of the mix as the reaction advances. Accordingly, when furfural is used as a solvent at high temperatures, the viscosity of the mix rapidly increases due to the reaction between furfural and the phenolic resin.
  • an aldehyde solvent such as benzaldehyde, reacts much more slowly than furfural with the phenolic resin and thus on mixing at high temperatures the viscosity increases less rapidly than when using furfural as a solvent.
  • the slower rate of reaction of the aldehyde solvent thus means that the aldehyde can be used to form the mixtures at higher temperatures and with a lesser amount of solvent to achieve the desired mixing viscosity. It will be readily appreciated by those skilled in the art that the use of a lesser amount of solvent will reduce environmental emissions.
  • the amount of aldehyde used as a solvent will be generally in the range of from 15 to 70% by weight based on the weight of the curable phenolic resin.
  • the phenolic resin which is used in the present invention is preferable a novolak resin such as are well known in the art.
  • the phenolic resin is preferably used in an amount of from 1 to 10% by weight based on the weight of the refractory materials, more preferably 2 to 6% by weight based on the weight of refractory materials. It will be understood by those skilled in the art that the amount of phenolic resin used in the present invention may require to be varied according to the particle size of the refractory materials and the particular properties desired in the articles which are to be produced according to the invention.
  • the process of the present invention may be used to manufacture shaped refractory articles from any refractory materials such as, for example, alumina, magnesia, graphite, zirconia, carbides, nitrides or other refractory ceramics materials, or mixtures thereof .
  • refractory materials such as, for example, alumina, magnesia, graphite, zirconia, carbides, nitrides or other refractory ceramics materials, or mixtures thereof .
  • a curing agent is preferably incorporated into the mixture from which the shaped refractory articles are prepared.
  • the curing agent may be present in the curable phenolic resin composition, or may be added to the mixture as a separate ingredient.
  • the temperature at which the mixture of refractory materials/resin and solvent is mixed will depend upon the amount of solvent and the amount of resin present in the mixture. However, generally the temperature will be in the range of from 30° to 100°C.
  • the mixing and drying of the refractory materials, phenolic resin and solvent is generally carried out for a time sufficient for the aldehyde solvent to react to some extent with the phenolic resin.
  • the reaction of the aldehyde with the resin results in a higher carbon residue being obtained on heating to high temperatures during the curing and carbonisation of the compression moulded articles. If the aldehyde solvent is not allowed a sufficient time to react with the phenolic resin then a larger proportion of the solvent will simply evaporate when the compression moulded articles are subsequently cured and carbonised. The loss of a higher proportion of solvent will result in a reduction in the carbon residue in the final moulded articles and/or increases porosity.
  • the mixing of the solvent with the phenolic binder and the refractory mixture will generally be carried out using standard mixing techniques. Mixing is continued until the refractory powdered materials are adequately coated. Further mixing is then generally carried out in order to agglomerate the powdered materials, with some evaporation of the aldehyde solvent optionally being carried out in order to produce agglomerates of the desired characteristics.
  • the mixture is generally dried sufficiently during this stage for the agglomerates, whilst being free-flowing, to possess a sufficient tack that when pressed they will bond together sufficiently for articles to be formed therefrom.
  • the compression moulding of the refractory mixture is carried out according to techniques standard in the art and, following moulding, the articles are then cured and carbonised. Curing is generally carried out at a temperature in the range of from 100° to 250°C, whilst the firing of the articles to effect carbonisation is generally carried out at a temperature in the range of from 600° to 1200°C.
  • Curing is generally carried out at a temperature in the range of from 100° to 250°C
  • the firing of the articles to effect carbonisation is generally carried out at a temperature in the range of from 600° to 1200°C.
  • the material was then tumbled in a mixer and partially dried by passing heated air at 90°C over the mix for a period of about 40 minutes.
  • the mixture was then cooled, a rubber mould was then filled with the mixture, sealed and isostatically pressed at 70000 kPa. The pressure was then slowly released to atmospheric over a period of 15 minutes.
  • the refractory article was then cured and carbonised by firing at a 1000°C.
  • a comparison of furfural and benzaldehyde as a solvent for a novolak resin was made by adding 20g of the solvent to 30g of a novolak resin (Borden TPSX4) .
  • the novolak resin also contained 10.5% by weight hexamine curing agent and 3 to 5% by weight of free phenol.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Procédé de fabrication d'articles réfractaires façonnés, ce qui consiste à mélanger un ou plusieurs matériaux réfractaires pulvérulents avec une résine phénolique durcissable et à ajouter au mélange un aldéhyde en tant que solvant de la résine phénolique durcissable ou à ajouter aux matériaux réfractaires pulvérulents, une résine phénolique durcissable dissoute dans un solvant d'aldéhyde comprenant un composé représenté par la formule générale (I), dans laquelle A, B, X, Z représentent certains groupes substituants définis, à sécher partiellement le mélange afin d'obtenir des agglomérats coulants du ou des matériaux pulvérulents et à soumettre ces agglomérats à un moulage par compression.
PCT/GB1996/002546 1995-10-17 1996-10-17 Procede de fabrication de materiaux refractaires WO1997014663A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU73127/96A AU7312796A (en) 1995-10-17 1996-10-17 Process for the manufacture of refractory materials

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9521215.5 1995-10-17
GBGB9521215.5A GB9521215D0 (en) 1995-10-17 1995-10-17 Process for the manufacture of refractory materials

Publications (1)

Publication Number Publication Date
WO1997014663A1 true WO1997014663A1 (fr) 1997-04-24

Family

ID=10782409

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/002546 WO1997014663A1 (fr) 1995-10-17 1996-10-17 Procede de fabrication de materiaux refractaires

Country Status (3)

Country Link
AU (1) AU7312796A (fr)
GB (1) GB9521215D0 (fr)
WO (1) WO1997014663A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2399987A1 (fr) * 1977-08-12 1979-03-09 Kurosaki Refractories Co Brique refractaire et son procede de fabrication
GB2096985A (en) * 1981-04-16 1982-10-27 Gen Refractories Co Carbon containing refractory bricks and shapes and methods of making such bricks and shapes
EP0164139A1 (fr) * 1984-04-26 1985-12-11 Hoogovens Groep B.V. Procédé de fabrication de briques réfractaires contenant du CaO
EP0270377A2 (fr) * 1986-12-04 1988-06-08 Borden (Uk) Limited Procédé de fabrication de corps réfractaires

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2399987A1 (fr) * 1977-08-12 1979-03-09 Kurosaki Refractories Co Brique refractaire et son procede de fabrication
GB2096985A (en) * 1981-04-16 1982-10-27 Gen Refractories Co Carbon containing refractory bricks and shapes and methods of making such bricks and shapes
EP0164139A1 (fr) * 1984-04-26 1985-12-11 Hoogovens Groep B.V. Procédé de fabrication de briques réfractaires contenant du CaO
EP0270377A2 (fr) * 1986-12-04 1988-06-08 Borden (Uk) Limited Procédé de fabrication de corps réfractaires

Also Published As

Publication number Publication date
GB9521215D0 (en) 1995-12-20
AU7312796A (en) 1997-05-07

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